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Wacaw Grzybkowski
CONDUCTOMETRIC
AND
POTENTIOMETRIC TITRATION
Gdask 2002
CONTENTS
1. TITRATION
2. CONDUCTOMETRIC TITRATION
3. POTENTIOMETRY
3.1 pH measurements
3.2 Potentiometric titration
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14
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TITRATION
titrations, complex-formation titrations, and oxidation-reduction (redox) titrations. In acid-base titration (i.e., the titration of an acid with a base, or vice versa), the
indicator is a substance that can exist in two forms, an acid form and a basic form,
which differ in colour. For example, litmus is blue in alkaline solution and red in acid
solution. Phenolphthalein is colourless in acid solution and pink in alkaline solution. A
wide choice of acid-base indicators is available, varying not only in the colours of the
two forms but also in the pH value at which the colour occurs.
Precipitation titrations may be illustrated by the example of the determination
of chloride content in a sample by titration with silver nitrate, which precipitates the
chloride in the form of silver chloride. The presence of the first slight excess of silver
ion (i.e., the end point) can be marked by the appearance of a coloured precipitate.
One way in which this can be done is by employing potassium chromate(VI) as the
indicator. Potassium chromate reacts with the first slight excess silver ion to form a
red precipitate of silver chromate. Another method involves the use of an adsorption
indicator, the indicator action being based on the formation on the surface of the
precipitate of an adsorbed layer of silver indicator salt, which forms only when an
excess of silver ions is present.
The most important titrations based upon complex-formation reactions are
those
involving
the
titration
of
metal
ions
with
the
reagent
disodium
conductometric
titrations, the electrical conductance or resistance of the solution being titrated; and
amperometric titrations, the electric current passing during the course of the
titration. In the
CONDUCTOMETRIC TITRATION
i=
U
R
G=
1
R
and is expressed in siemens [S], that is in ohms-1 [1] or mhos. The conductance of
a homogeneous body of uniform cross section is proportional to the cross section A
and inversely proportional to the length l :
G=
A
l
k
R
1000
c
where c is the molar concentration, that is expressed in moldm-3. 1000 is the factor
arising from the fact that 1 dm3=1000 cm3. Thus, the molar conductance is expressed
in Scm2mol-1. The molar conductance is sometimes described as the actual
conductance of that volume of solution which contains one mol of solute when placed
between parallel electrodes 1 cm apart with a uniform electric field between them. In
order to compare the conductances of the electrolytes differing in the ionic
composition the equivalent conductance eq is defined
eq =
1000
c eq
= 0 c
[ ]
[ ]
0 [HCl] = 0 H+ + 0 Cl
[ ]
0 [H2 SO 4 ] = 2 0 H + + 0 SO 24
For weak electrolytes, thus for weakly ionized solutes, varies markedly with
concentration because the degree of dissociation varies strongly with concentration.
The limiting molar conductances of weak electrolytes we can calculate with the help
of the law of independent migration of ions. Thus, for acetic acid, we can write:
[ ]
[ ]
[ ]
[ ]
= 0 H + + 0 CH3 COO _ + 0 Na + 0 Na + + 0 Cl 0 Cl
= 0 [HCl] + 0 [CH3 COONa] 0 [NaCl]
For sufficiently weak electrolytes, the ionic concentration is small and the
effect of ion attraction on the mobilities is slight; thus we may assume the mobilities
to be independent of concentration and obtain the approximate equation
which may be used to calculate the value of fractional ionization , known also as
the degree of dissociation. If one measures for a weak electrolyte at concentration
c and calculates from conductometric data for strong electrolyte or from known
values of the limiting conductances of the individual ions, it is possible to obtain the
actual degree of ionization of the weak electrolyte at this concentration. Then the
value of respective equilibrium constant, KC, can be estimated using the Ostwalds
Dilution Law
KC =
2c
1
current, so that the quantity of the electricity carried during one half cycle is insufficient to produce any measurable polarization, and at the same time by (2) employing
platinum covered with platinum black, having an extremely large surface area, to
facilitate the adsorption of the tiny quantities of electrode reaction products produced
in one-half cycle, hence, reducing the polarization effect.
Classical circuit employed to such measurements is a Wheatstone Bridge
adapted for use of a high frequency alternating current. However, a variable
capacitance is necessary to achieve a true balance and eliminate the non-ohmic
effects.
Determination of the ac impedance can be also carried out with an automatic
bridge that employs a frequency generator and gives a direct read-out. Such an
equipment is employed for measurements during conductometric titration.
In all measurements of impedance, careful temperature control is essential,
since viscosity of water, for example, changes in the region near room temperature
by about of 3% per degree.
It was mentioned above that the measured conductance of an electrolyte
solution depends primarily on the concentration and types of the ions. Conductivity
measurement can thus provide a sensitive measure of the changes taking place in
ionic composition in the course of chemical reaction occurring in the solution during
conductometric titration.
Consider a solution of a strong acid, hydrochloric acid, HCl for instance, to
which a solution of a strong base, sodium hydroxide NaOH, is added. The reaction
H+ + OH H2 O
occurs. For each amount of NaOH added equivalent amount of hydrogen ions is
removed. Effectively, the faster moving H+ cation is replaced by the slower moving
Na+ ion, and the conductivity of the titrated solution as well as the measured
conductance of the cell fall. This continues until the equivalence point is reached, at
which we have a solution of sodium chloride, NaCl. If more base is added an
increase in conductivity or conductance is observed, since more ions are being
added and the neutralization reaction no longer removes an appreciable number any
of them. Consequently, in the titration of a strong acid with a strong base, the
conductance has a minimum at the equivalence point. This minimum can be used
instead of an indicator dye to determine the endpoint of the titration. Conductometric
titration curve, that is a plot of the measured conductance or conductivity values
against the number of milliliters of NaOH solution, is shown in Fig. 2.
Fig.2. Conductometric titration curve for hydrochloric acid titrated using solution of
sodium hydroxide.
The position of the equivalence point may be localized precisely as the point of
intersection of two straight-lines both determined using readings obtained before and
after the minimum observed, respectively. It makes the conductometric titration more
objective and independent of a nature of an indicator used in the end-point method.
This is one of advantages of the instrumental method.
The same reaction of neutralization takes place when a solution of strong base
is titrated using a solution of strong acid. Thus, analogous effects and very similar
shape of conductometric titratration curve are observed.
Consider the titration of solution of weak acid, such as acetic acid CH3COOH,
using a solution of strong base, NOH. As we know, the weak acids, as well as other
weak electrolytes, are dissociated into very small extent and they exist in solution
essentially in form of the neutral acid molecules. When a solution of NaOH is added
the reaction occurs
CH3 COOH + Na + + OH- Na + + CH3 COO + H2 O
and, as is seen, the undissociated molecules of acetic acid are transformed into
dissociated molecules of potassium acetate. The changes are accompanied by
increase in conductivity of the solution, Figure 3.
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Fig.3. Conductometric titration curve for acetic acid titrated using solution of sodium
hydroxide.
This minor
H2 O
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Fig.4. Conductometric titration curve for the hydrochloric acid acetic acid mixture
titrated using solution of sodium hydroxide.
HC2O 4 H+ + C2O 4
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The dissociation constant for the second proton is significantly smaller, and so
pK2 > pK1. Hence, the solution of the oxalic acid may be considered as an equimolar
mixture of two acids of differing strength.
The dissociation constant for the second proton is significantly smaller, and so
pK2 > pK1. Hence, the solution of the oxalic acid may be considered as an equimolar
mixture of two acids of differing strength.
It seems to be rather obvious that an analogous conductometric titration curve
describes a conductometric titration of solution of weak base, such as ammonia,
using a solution of strong acid.
The conductometric titration method can also be employed in other volumetric
estimations, e.g. the determination of halides by titration with silver nitrate.
Correction for the relatively small change of volume during the titration is
readily made by plotting not the measured conductance or conductivity, but the
values of product of the conductance and total volume of the sample, against the
volume of titrant added.
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POTENTIOMETRY
pH MEASUREMENT
Perhaps the most common potentiometric measurement is that of pH. pH was
pH =
E + E(cal)
( RT / F) ln10
pH =
E + E(cal)
( 59,16 mV )
or at temperature of 250C
pH ( X) = pH (S)
E
(RT / F) ln10
pH ( X) = pH (S)
E
( 59.16 mV )
or
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and S is a solution of standard pH while || 3.5 MKCl (aq) || denotes the salt bridge. The
currently recommended primary standards include a saturated solution of potassium
hydrogen tartrate, which has pH =3.557 at 250C and 0.0100 mol kg-1 disodium
tetraborate, which has pH=9.180 at that temperature.
In practice, indirect methods are much more convenient, and the hydrogen
electrode is replaced by the glass electrode. This electrode is sensitive to hydrogen
ion and its potential is proportional to pH. It is filled with hydrochloric acid or
phosphate buffer containing Cl anions. Conveniently, the glass electrode has E=0
when the external medium is at pH=7.The glass electrode is much more convenient
to handle than the gas electrode itself, and can be calibrated using solutions of
known pH. The glass electrode is usually used in conjunction with a calomel
electrode that makes contact with the test solution through a salt bridge.
Fig.1. Glass electrode and its cell schematic in association with a reference electrode
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The
sensitivity
of
glass
electrode
towards
hydrogen
( H+ )
or
POTENTIOMETRIC TITRATION
If, during a chemical reaction, there is a change in the concentration of an ion
which can be sensed through the change in potential of a suitable electrode, then the
progress of the reaction can be followed through this potential change. It follows the
electromotive force measurements, like conductivity measurements, can serve to
determine the equivalence point or end point of titration. Both conventional
electrodes and the types of ion-sensitive electrodes can be used to follow the
process and the change of potential in the case of acid-base, precipitation,
complexation and red-ox titration.
To follow an acid-base titration a hydrogen electrode or a pH-sensitive glass
electrode may be used as the indicator electrode. In both cases, as the titration is
carried
difference measured will decrease at the rate of 59.1 mV per decade lowering in
H3O+ concentration. As long as the acid is in excess, then the pH, as well as the
electromotive force of the studied cell, will vary only slightly with addition of base.
However, near the equivalence point, concentration of the H3O+ cation falls rapidly
before levelling out again in excess base. Thus, the measured potential difference
will show a step-like behaviour, as is seen in Figure 1,
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in which the change in potential of the pH-electrode is calculated for titration of 100
cm3 of 0.01 M solution of strong acid, HCl, with 0.1 M solution of strong base. The
end-point of the titration corresponds to the point at which the potential changes most
rapidly.
Fig.2. Potentiometric acid-base titration: (a) schematic representation of titration of 100 cm3 of a
strong acid of concentration 0.01 M with a stronge base of concentration 0.1 M; (b) differential
potential change on addition of aliquots of titrant, showing a marked peak at the end point.
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A more precise measure of the end-point than the position of the steepest
change in the potential difference, i.e. the change in the electromotive force, can be
obtained by plotting the derivative of the potential difference with the volume of titrant
added. This is shown as the dotted line in Figure 2, and it can be see to have a nice,
sharp maximum indicating a position of the end-point.
As an example of the precipitation titration, consider the determination of the
chloride ions by silver nitrate, making use of the reaction
Ag + + Cl AgCl(s)
here, the equilibrium-potential of the Ag|Ag+ electrode can be followed as a function
of addition of the titrant. At the beginning of the titration, the concentration of silver in
solution will, in effect, be determined by the solubility product of silver chloride, and,
at the end-point, the Ag+ concentration will rise very rapidly as the last of the chloride
is precipitated. The height of the potential step can be further enhanced if the
titrations is carried out in a water-acetone mixture, in which the solubility of silver
chloride is lower.
The change of potential in the case of complexation and redox titrations is
very similar to that observed in case of potentiometric acid-base and precipitation
titration.
Potentiometric titrations have the great advantage, in common with
conductometric titrations, of being possible in turbid, coloured and very dilute
solutions. Further advantages of potentiometric titrations are the generally very sharp
end points and the ease of automation, and a large number of commercial rigs are
available. The range of applications is enormous, and accurate methods have been
developed for many electroanalytical processes.
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